Sulphonated mixed ketones



Patented Aug. 3, 1937 UNITED STATES SULPHONATED MIXED KETONES Anderson W. Balaton, Chicago, Ill., assignor to Armour and Company, Chicago, 11]., a corporation of Illinois No Drawing. Application May z'i, 1936, Serial No. 82,140

. 10Cla'ims.

This invention relates to sulphonated ketones of the type BC-B' wherein R is an aryl or heterocyclic radical and R is an alkyl radical containing at least six carbon atoms, the ketone containing at least two sulphonic acid radicals or salts thereof.

Within recent years various detergent compounds unrelated to the ordinary fatty acid soaps have been prepared. Although the ordinary soaps are good detergents they are not effective in so-called hard waters or waters containing calcium salts. Consequently, much experimental work has been devoted toward the development of detergentsand wetting-out agents which would be operative equally well in. hard and soft waters. Perhaps one of the first substances proposed for use in hard water was a sulphonated castor oil and the sulphonated fatty oils have been widely used as wetting-out agents in textile finishing and dyeing. Such sulphonated fatty oils are, however, not generally uniform from batch to batch and this is in part due to variations in the fatty oil raw material and to sulphonating conditions.

More recently various sulphonated alcohols and sulphated alcohols have been used as detergents, wetting-out agents, and foaming agents, and these materials have enjoyed marked commercial success. Still more recently, as in U.'S. Patent 2,037,974, sulphonated aliphatic ketones have been prepared for use in the arts.

I have now been able to prepare a new'class of sulphonated compounds which have properties, both physical and chemical, which make them superior to the sulphonated materials hitherto used in the arts. My sulphonated compounds are extremely effective in waters containing relatively large amounts of calcium and magnesiumsalts. One very real advantage in my compounds is that the basic starting material to be sulphonated can be prepared in a highly pure state. This means that the sulphonated compounds are not contaminated with unsuiphonated impurities of unknown constitution. Moreover, the extent of sulphonation can be controlled readily which is desirable in this art. The sulphonated products of my invention form water soluble salts of both the alkali and alkaline earth metals, both of which classes of salts possess detergent and wetting-out properties.

My compounds can be generically described as mixed ketones of the type wherein R is an aryl or heterocyclicradical and R is an alkyl radical containing at least six carbon atoms, which ketones have been sulphonated to a degree which introduces at least two sulphonic acid radicals. Frequently my compounds contain three or more sulphonic radicals distributed between the aryl and alkyl radicals. Invariably, at least one sulphonic acid radical will appear in the alkyl radical regardless of how many sulphonic acid radicals have been introduced.

Since there are many sulphonic acid compounds falling within the generic disclosure of my invention, I shall not attempt to list them all. I give, however, in the following table, a representative list of ketones which can be sulphonated to form products of my invention. I shall then describe examples of sulphonating a representative group of these ketones.

Some of the ketones which I sulphonate are:

Heptadecyl phenyl ketone Heptadecylp-tolyl ketone Heptadecyl m-xylyl ketone Heptadecyl p-xlyly ketone Pentadecyl m-xylyl ketone Pentadecyl p-tolyl ketone p-Methoxyphenyl pentadecyl ketone p-Ethoxyphenyl pentadccyl ketone Phenyl undecyl ketone p-Chlorphenyl undecyl ketone p-Methoxyphenyl heptadecyl ketone p-Me'thoxyphenyl undecyl ketone p-Phenoxyphenyl heptadecyl ketone p-Phenoxyphenyl tridecyl ketone p-Phenoxyphenyl undecyl ketone p-Nitro phenoxyphenyl heptadecyl ketone p-Methyl phenoxyphenyl heptadecyl ketone Alkyl phenones from lard fatty acids Alpha naphthyl heptadecyl ketone Alpha naphthyl pentadecyl ketone Anthracyl heptadecyl ketone (mixtures) Biphenyl heptadecyl ketone Biphenyl tridecyl ketone Biphenyl undecyl ketone p-Methyl biphenyl heptadecyl ketone p-Chlorbiphenyl heptadecyl ketone Fury] heptadecyl ketone Furyl undecyl ketone Methyl furyl heptadecyl ketone Dibenzofuryl heptadecyl ketone Dibenzofuryl undecyl ketone Also ketones wherein the heterocyclic radical is derived from carbazol, thiophene and fluorene.

Most of the ketones which I sulphonate will contain at least 10 or 11 carbon atoms in the alkyl group but I do not intend to be limited to this as the lower number of carbon atoms. I can sulphonate mixed ketones in which the alkyl radical contains six, seven, eight, and nine carbon atoms and get sulphonated products Wi'iiCh have fairly satisfactory detergent properties. However, better products and better results are obtained when the alkyl group contains at least eleven carbon undecyl ketone.

- most always start with a ketone in which the pensive and give good results.

acid derivative 'of theketone precipitates.

alkyl radical is heptadecyl since this radical is readily obtained from stearic acid and inexpensive fatty acid sources. Many of the ketones which I sulphonate are new compounds per se and have but recently been described in U. 3. Patents 2,033,540, 2,033,541, and 2,033,542.

The above list of ketone starting materials is given largely for the purpose of indicating the generic characteristics of my invention. Many of these ketones, especially-the heterocyclic compounds would not ordinarily be sulphonated simply because the aralkyl ketones are less ex- However, the broad class of compounds is new with .me and I do not wish to be limited to any specific member except insofar as the prior art may dictate.

Since my disclosure would be extended far beyond. ordinary requirements were I todescribe the sulphonation of all of the above-listed ketones, and sulphonation processes are generally understood in the art anyway, I shall bri eflyjdescribe the sulphonation of diphenylheptadecyl ketone.

I find that chlorosulphonic acid is a particularly advantageous sulphonating agent to use since it insures the introduction of at least two sulphonic acid radicals. agents can, of course, be used, any my'invention is not restricted to any particular sulphonating process since-these are generally well known in the art.

Thus, for example, I add 80 grams of diphenylheptadecyl ketone to 300 cubic centimeters of chlorosulphonic acid and, by cooling, maintain the reaction temperature at about 5 C. The

'ketone should be added slowly with agitation.

After all of it has been added, I heat the reaction mixture at 30 to 40 0., for about six hours, then allow to cool and .pour on ice. The sulphonic Advantageously it is collected on a filter, washed with dilute hydrochloric acid and dried. It can be further purified by dissolving it in water and reprecipitating it by the addition of hydrochloric acid to the water solution.

Analysis for sulphur shows a content of about 14.3 percent. This corresponds with the introduction of three sulphonicacid radicals. When methods for determining the position of the sul- 1 phonic acid radicals are used, I find that one of the radicals is in the aromatic diphenyl group and two are in the alkyl group. Sulphonating conditions can, of course, be so controlled that only two sulphonic acid radicals are introduced but invariably one willbe in the alkyl radical of the ketone. For example, by decreasing the quantity of chlorosulphonic acid and the reaction time and temperature, I can stop the sulphona-' Other sulphonating ketone, as well as all other sulphonated ketones of the type defined form water-soluble alkaliiorming metal salts such as the sodium and calcium salts. These can be prepared by simply adding the appropriate alkali to a water solution of the free acid, or by dissolving the free acid in a water solution of the alkali.

As a further example, I treat 80 grams of phenoxyphenyl heptadecyl'ketone with 300 cubic centimeters of chlorosulphonic acid in the manner described above. This gives me a tri-sulphonic acid compound. Under similar operating conditions and with the approximate quantities stated naphthylheptadecyl ketone, phenylheptadecyl ketone, and dibenzofuryl heptadecyl ketone all give sulphonic acid derivatives which are-water soluble when at least two sulphonic acid radicals have been introduced, and which give solutions having good foaming and detergent properties.

All of my sulphonated ketones can be used in soap mixtures to enhance foaming and to improve the detergent action in hardwaters.

Although the art is primarily interested in the free sulphonic acid compounds and their alkaliforming metal salts, other metal-salts, such as the copper salts, may have utility in the arts in various relations and I do not wish to limit the scope of my claims to the free acid and its alkali-forming metal salts.

Having thus described my invention what I claim is: I

1. A sulphonated ketone having the formula wherein R. is a member of the group consisting of aryl and heterocyclic radicals and R is an alkyl radical containing at least six carbon atoms, the ketone containing at least two SO:X groups at least one of which is in the aiml radical and wherein X is a member of the group consisting of hydrogen, and metals.

2. A sulphonated ketone having the formula wherein R is a member of the group consisting of aryl and heterocyclic radicals and R is an alkyl radical containing at least six carbon atoms, the ketone containing at least two -SO3X groups at least one of which is in the alkyl radical and wherein X is an alkali-forming metal.

, 3. A sulphonated ketone having the formula wherein R is a member of the group consisting of aryl and heterocyclic radicals and R is an alkyl radical containing at least six carbon atoms, the ketone containing at least two SOaX groups at least one of which is in the alkyl radical and wherein X is'sodium.

4. A sulphonated ketone having the formula wherein R is an aryl or heterocyclic radical and R. is an alhl radical containing at least six carbon atoms, the ketone'containing at least two sulphonic acid groups one of which is in the alkyl radical.

5. A sulphonated aralkyl ketone containing at least two sulphonic acid radicals one of which is in the alkyl radical of the ketone, said alkyl radical containing at least six carbon atoms.

6. A trisulphonic acid. of an aralkyl ketone 8. A trisulphonlc acid of an arylheptadecyl having at least six carbon atoms in the alkyl ketone. radical, at least one of the sulphonic acid radicals 9. A trisulphonic acid of dlphenyl heptadecyl being in the alkyl radical. ketone.

7. A sulphonated aryl heptadecyl ketone con- 10. A trisulphomc acid of phenyl heptadecyl 5 taming at least two sulphonic acid radicals one ketone. a of which is in the heptadecyl radical. ANDERSON W. RALS'ION. 

